Reaction of carbon monoxide and hydrogen on neutral Nb8 clusters in the gas phase
Reactions of neutral V(n), Nb(n), and Ta(n) metal clusters (n< or =11) with CO+H(2) mixed gases and CH(3)OH in a flow tube reactor (1-50 Torr) are studied by time of flight mass spectroscopy and density functional theory calculations. Metal clusters are generated by laser ablation, and reactants...
Gespeichert in:
Veröffentlicht in: | The Journal of chemical physics 2008-01, Vol.128 (4), p.044306-044306 |
---|---|
Hauptverfasser: | , , , |
Format: | Artikel |
Sprache: | eng |
Online-Zugang: | Volltext |
Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
container_end_page | 044306 |
---|---|
container_issue | 4 |
container_start_page | 044306 |
container_title | The Journal of chemical physics |
container_volume | 128 |
creator | Xie, Y He, S-G Dong, F Bernstein, E R |
description | Reactions of neutral V(n), Nb(n), and Ta(n) metal clusters (n< or =11) with CO+H(2) mixed gases and CH(3)OH in a flow tube reactor (1-50 Torr) are studied by time of flight mass spectroscopy and density functional theory calculations. Metal clusters are generated by laser ablation, and reactants and products are ionized by low fluence (approximately 200 microJ/cm(2)) 193 nm excimer laser light. Nb(n) clusters exhibit strong size dependent reactivity in reactions both with CO+H(2) and CH(3)OH compared with V(n) and Ta(n) clusters. A "magic number" (relatively intense) mass peak at Nb(8)COH(4) is observed in the reaction of Nb(n) clusters with CO+H(2), and CH(3)OH is suggested to be formed. This feature at Nb(8)COH(4) remains the most intense peak independent of the relative concentrations of CO and H(2) in the flow tube reactor. No other Nb(n), Ta(n), or V(n) feature behaves in this manner. In reactions of CH(3)OH with metal clusters M(n) (M=V, Nb, and Ta, n=3-11), nondehydrogenated products M(n)COH(4)/M(n)CH(3)OH are only observed on Nb(8) and Nb(10), whereas dehydrogenated products M(n)CO/CM(n)O are observed for all other clusters. These observations support the suggestion that CH(3)OH can be formed on Nb(8) in the reaction of Nb(n) with CO+H(2). A reaction mechanism is suggested based on the experimental results and theoretical calculations of this work and of those in the literature. Methanol formation from CO+H(2) on Nb(8) is overall barrierless and thermodynamically and kinetically favorable. |
doi_str_mv | 10.1063/1.2813348 |
format | Article |
fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_70268272</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>70268272</sourcerecordid><originalsourceid>FETCH-LOGICAL-c198t-cb40618c423a073e9d63b0e26cdab52656333509ea9b2947a5e488a70dadcc7b3</originalsourceid><addsrcrecordid>eNpFkEtLw0AUhQdRbK0u_AMyK8FF6p2ZZB5LKb6gKIquwzxu20ia1JkE7L830oCrc-B8nMVHyCWDOQMpbtmcayZEro_IlIE2mZIGjskUgLPMSJATcpbSFwAwxfNTMmGa58rkekre3tH6rmob2q6ot9ENbds27U8VkNom0M0-xHaNw97QBvsu2pq-OE193acOY6JVQ7sN0rVNdLexCc_JycrWCS_GnJHPh_uPxVO2fH18XtwtM8-M7jLvcpBM-5wLC0qgCVI4QC59sK7gspBCiAIMWuO4yZUtMNfaKgg2eK-cmJHrw-8utt89pq7cVsljXdsG2z6VCrjUXPEBvDmAPrYpRVyVu1htbdyXDMo_fyUrR38DezWe9m6L4Z8chYlfJJZpfw</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>70268272</pqid></control><display><type>article</type><title>Reaction of carbon monoxide and hydrogen on neutral Nb8 clusters in the gas phase</title><source>AIP Journals Complete</source><source>AIP Digital Archive</source><source>Alma/SFX Local Collection</source><creator>Xie, Y ; He, S-G ; Dong, F ; Bernstein, E R</creator><creatorcontrib>Xie, Y ; He, S-G ; Dong, F ; Bernstein, E R</creatorcontrib><description>Reactions of neutral V(n), Nb(n), and Ta(n) metal clusters (n< or =11) with CO+H(2) mixed gases and CH(3)OH in a flow tube reactor (1-50 Torr) are studied by time of flight mass spectroscopy and density functional theory calculations. Metal clusters are generated by laser ablation, and reactants and products are ionized by low fluence (approximately 200 microJ/cm(2)) 193 nm excimer laser light. Nb(n) clusters exhibit strong size dependent reactivity in reactions both with CO+H(2) and CH(3)OH compared with V(n) and Ta(n) clusters. A "magic number" (relatively intense) mass peak at Nb(8)COH(4) is observed in the reaction of Nb(n) clusters with CO+H(2), and CH(3)OH is suggested to be formed. This feature at Nb(8)COH(4) remains the most intense peak independent of the relative concentrations of CO and H(2) in the flow tube reactor. No other Nb(n), Ta(n), or V(n) feature behaves in this manner. In reactions of CH(3)OH with metal clusters M(n) (M=V, Nb, and Ta, n=3-11), nondehydrogenated products M(n)COH(4)/M(n)CH(3)OH are only observed on Nb(8) and Nb(10), whereas dehydrogenated products M(n)CO/CM(n)O are observed for all other clusters. These observations support the suggestion that CH(3)OH can be formed on Nb(8) in the reaction of Nb(n) with CO+H(2). A reaction mechanism is suggested based on the experimental results and theoretical calculations of this work and of those in the literature. Methanol formation from CO+H(2) on Nb(8) is overall barrierless and thermodynamically and kinetically favorable.</description><identifier>ISSN: 0021-9606</identifier><identifier>EISSN: 1089-7690</identifier><identifier>DOI: 10.1063/1.2813348</identifier><identifier>PMID: 18247948</identifier><language>eng</language><publisher>United States</publisher><ispartof>The Journal of chemical physics, 2008-01, Vol.128 (4), p.044306-044306</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c198t-cb40618c423a073e9d63b0e26cdab52656333509ea9b2947a5e488a70dadcc7b3</citedby><cites>FETCH-LOGICAL-c198t-cb40618c423a073e9d63b0e26cdab52656333509ea9b2947a5e488a70dadcc7b3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,782,786,27931,27932</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/18247948$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Xie, Y</creatorcontrib><creatorcontrib>He, S-G</creatorcontrib><creatorcontrib>Dong, F</creatorcontrib><creatorcontrib>Bernstein, E R</creatorcontrib><title>Reaction of carbon monoxide and hydrogen on neutral Nb8 clusters in the gas phase</title><title>The Journal of chemical physics</title><addtitle>J Chem Phys</addtitle><description>Reactions of neutral V(n), Nb(n), and Ta(n) metal clusters (n< or =11) with CO+H(2) mixed gases and CH(3)OH in a flow tube reactor (1-50 Torr) are studied by time of flight mass spectroscopy and density functional theory calculations. Metal clusters are generated by laser ablation, and reactants and products are ionized by low fluence (approximately 200 microJ/cm(2)) 193 nm excimer laser light. Nb(n) clusters exhibit strong size dependent reactivity in reactions both with CO+H(2) and CH(3)OH compared with V(n) and Ta(n) clusters. A "magic number" (relatively intense) mass peak at Nb(8)COH(4) is observed in the reaction of Nb(n) clusters with CO+H(2), and CH(3)OH is suggested to be formed. This feature at Nb(8)COH(4) remains the most intense peak independent of the relative concentrations of CO and H(2) in the flow tube reactor. No other Nb(n), Ta(n), or V(n) feature behaves in this manner. In reactions of CH(3)OH with metal clusters M(n) (M=V, Nb, and Ta, n=3-11), nondehydrogenated products M(n)COH(4)/M(n)CH(3)OH are only observed on Nb(8) and Nb(10), whereas dehydrogenated products M(n)CO/CM(n)O are observed for all other clusters. These observations support the suggestion that CH(3)OH can be formed on Nb(8) in the reaction of Nb(n) with CO+H(2). A reaction mechanism is suggested based on the experimental results and theoretical calculations of this work and of those in the literature. Methanol formation from CO+H(2) on Nb(8) is overall barrierless and thermodynamically and kinetically favorable.</description><issn>0021-9606</issn><issn>1089-7690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2008</creationdate><recordtype>article</recordtype><recordid>eNpFkEtLw0AUhQdRbK0u_AMyK8FF6p2ZZB5LKb6gKIquwzxu20ia1JkE7L830oCrc-B8nMVHyCWDOQMpbtmcayZEro_IlIE2mZIGjskUgLPMSJATcpbSFwAwxfNTMmGa58rkekre3tH6rmob2q6ot9ENbds27U8VkNom0M0-xHaNw97QBvsu2pq-OE193acOY6JVQ7sN0rVNdLexCc_JycrWCS_GnJHPh_uPxVO2fH18XtwtM8-M7jLvcpBM-5wLC0qgCVI4QC59sK7gspBCiAIMWuO4yZUtMNfaKgg2eK-cmJHrw-8utt89pq7cVsljXdsG2z6VCrjUXPEBvDmAPrYpRVyVu1htbdyXDMo_fyUrR38DezWe9m6L4Z8chYlfJJZpfw</recordid><startdate>20080128</startdate><enddate>20080128</enddate><creator>Xie, Y</creator><creator>He, S-G</creator><creator>Dong, F</creator><creator>Bernstein, E R</creator><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20080128</creationdate><title>Reaction of carbon monoxide and hydrogen on neutral Nb8 clusters in the gas phase</title><author>Xie, Y ; He, S-G ; Dong, F ; Bernstein, E R</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c198t-cb40618c423a073e9d63b0e26cdab52656333509ea9b2947a5e488a70dadcc7b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2008</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Xie, Y</creatorcontrib><creatorcontrib>He, S-G</creatorcontrib><creatorcontrib>Dong, F</creatorcontrib><creatorcontrib>Bernstein, E R</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>The Journal of chemical physics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Xie, Y</au><au>He, S-G</au><au>Dong, F</au><au>Bernstein, E R</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Reaction of carbon monoxide and hydrogen on neutral Nb8 clusters in the gas phase</atitle><jtitle>The Journal of chemical physics</jtitle><addtitle>J Chem Phys</addtitle><date>2008-01-28</date><risdate>2008</risdate><volume>128</volume><issue>4</issue><spage>044306</spage><epage>044306</epage><pages>044306-044306</pages><issn>0021-9606</issn><eissn>1089-7690</eissn><abstract>Reactions of neutral V(n), Nb(n), and Ta(n) metal clusters (n< or =11) with CO+H(2) mixed gases and CH(3)OH in a flow tube reactor (1-50 Torr) are studied by time of flight mass spectroscopy and density functional theory calculations. Metal clusters are generated by laser ablation, and reactants and products are ionized by low fluence (approximately 200 microJ/cm(2)) 193 nm excimer laser light. Nb(n) clusters exhibit strong size dependent reactivity in reactions both with CO+H(2) and CH(3)OH compared with V(n) and Ta(n) clusters. A "magic number" (relatively intense) mass peak at Nb(8)COH(4) is observed in the reaction of Nb(n) clusters with CO+H(2), and CH(3)OH is suggested to be formed. This feature at Nb(8)COH(4) remains the most intense peak independent of the relative concentrations of CO and H(2) in the flow tube reactor. No other Nb(n), Ta(n), or V(n) feature behaves in this manner. In reactions of CH(3)OH with metal clusters M(n) (M=V, Nb, and Ta, n=3-11), nondehydrogenated products M(n)COH(4)/M(n)CH(3)OH are only observed on Nb(8) and Nb(10), whereas dehydrogenated products M(n)CO/CM(n)O are observed for all other clusters. These observations support the suggestion that CH(3)OH can be formed on Nb(8) in the reaction of Nb(n) with CO+H(2). A reaction mechanism is suggested based on the experimental results and theoretical calculations of this work and of those in the literature. Methanol formation from CO+H(2) on Nb(8) is overall barrierless and thermodynamically and kinetically favorable.</abstract><cop>United States</cop><pmid>18247948</pmid><doi>10.1063/1.2813348</doi><tpages>1</tpages></addata></record> |
fulltext | fulltext |
identifier | ISSN: 0021-9606 |
ispartof | The Journal of chemical physics, 2008-01, Vol.128 (4), p.044306-044306 |
issn | 0021-9606 1089-7690 |
language | eng |
recordid | cdi_proquest_miscellaneous_70268272 |
source | AIP Journals Complete; AIP Digital Archive; Alma/SFX Local Collection |
title | Reaction of carbon monoxide and hydrogen on neutral Nb8 clusters in the gas phase |
url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-05T19%3A02%3A20IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Reaction%20of%20carbon%20monoxide%20and%20hydrogen%20on%20neutral%20Nb8%20clusters%20in%20the%20gas%20phase&rft.jtitle=The%20Journal%20of%20chemical%20physics&rft.au=Xie,%20Y&rft.date=2008-01-28&rft.volume=128&rft.issue=4&rft.spage=044306&rft.epage=044306&rft.pages=044306-044306&rft.issn=0021-9606&rft.eissn=1089-7690&rft_id=info:doi/10.1063/1.2813348&rft_dat=%3Cproquest_cross%3E70268272%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=70268272&rft_id=info:pmid/18247948&rfr_iscdi=true |